Poly(butylene adipate-co-terephthalate) (PBAT) and poly(lactic acid) (PLA) are well-known biodegadable polyesters due to their outstanding performance. The biodegradation behavior of PLA/PBAT blends in freshwater with sediment is investigated in this study by analyzing the appearance, chemical structure and aggregation structure of their degraded residues via SEM, TG, DSC, gel permeation chromatography (GPC) and XPS. The effect of aggregation structure, hydrophilia and biodegradation mechanisms of PBAT and PLA on the biodegradability of PLA/PBAT blends is illuminated in this work. After biodegradation, the butylene terephthalate unit in the molecular structure of the components and the molecular weight of PLA/PBAT blends decreased, while the content of C-O bond in the composites increased, indicating that the samples indeed degraded. After 24 months of degradation, the increase in the relative peak area proportion of C-O to C=O in PLA/PBAT-25, PLA/PBAT-50 and PLA/PBAT-75 was 62%, 46% and 68%, respectively. The biodegradation rates of PBAT and PLA in the PLA/PBAT blend were lower than those for the respective single polymers.
Poly(lactic acid) (PLA) and poly(glycolic acid) (PGA) are extensively studied biodegradable polymers. However, the degradation behavior of their copolymer, poly(lactic-co-glycolic acid) (PLGA), in marine environments has not yet been confirmed. In this study, the changes in macroscopic and microscopic morphology, thermal properties, aggregation, and chemical structure of PLA, PGA, PLGA-85, and PLGA-75 (with 85% and 75% LA content) in simulated marine environments were investigated. Results revealed that degradation occurred through hydrolysis of ester bonds, and the degradation rate of PGA was faster than that of PLA. The amorphous region degraded preferentially over the crystalline region, leading to cleavage-induced crystallization and decreased thermal stability of PLA, PLGA-85, and PLGA-75. The crystal structures of PLGAs were similar to those of PLA, and the higher GA content, the faster was the degradation rate. This study provides a deeper understanding of the seawater degradation behaviors of PLA, PGA, and their copolymers, and provides guidance for the preparation of materials with controllable degradation performance.
Poly (butylene adipate-co-terephthalate) (PBAT) and poly (butylene succinate) (PBS) are polyester materials with excellent biodegradability under soil and compost conditions. However, the research on their degradation process in the marine environment is scarce. In this study, a more realistic simulation marine environment with sediment and marine organisms was developed, followed by investigation of the biodegradation behavior of PBAT and PBS mulch in it. The effect of aromatic structure, carboxyl end group content, molecular weight, and inorganic fillers on the degeneration of mulch was characterized by the changes in appearance, chemical structure, thermal properties, and crystallinity via Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, gel permeation chromatography, element analysis, and X-ray photoelectron spectroscopy. The molecular weight of polyester blends decreased, while the content of the C-O bond in the composites increased, indicating that the samples indeed degraded. The degradation rate was measured with the CO2 release amount. The aliphatic polyester structure, lower molecular weight, higher carboxyl end group content, and the involvement of inorganic fillers facilitate the disintegration of polyester in the marine environment, which provides an effective method to construct materials with controllable biodegradable performance.
An antifouling epoxy resin doped with natural clay nanotubes that are loaded with biocide or silver allowed extended protection against the proliferation of marine microorganisms. Compared to the 2–3 months of protection with antifoulant dichlorooctylisothiazolone (DCOIT) directly admixed into epoxy resin, the DCOIT release time of the halloysite formulations was extended to 12 months by incorporating biocide-loaded nanoclay in the polymer matrix. The protective properties of the epoxy-halloysite nanocomposites showed much less adhesion and proliferation of marine bacteria Vibrio natriegens on the resin surface after a two-month exposure to seawater than the coating formulations directly doped with non-encapsulated DCOIT. The coating formulation protection efficiency was further confirmed by twelve-month shallow field tests in the South China Sea. Replacing 2 wt.% biocide in the traditional formula with DCOIT-loaded natural environmentally friendly halloysite clay drastically improved the antifouling properties of the epoxy coating, promising scalable applications in protective marine coating. The antifouling property of epoxy resin was enhanced with silver particles synthesized on halloysite nanotubes. A natural mixture of MnO particles and halloysite could also be used as a nonbiocide additive to marine coating. The short-term White Sea water test of epoxy coating with 5% of Ag-halloysite composite of MnO-halloysite natural mixture showed no visible fouling.